CN107337454B - A kind of preparation method of silicon nitride composite powder - Google Patents
A kind of preparation method of silicon nitride composite powder Download PDFInfo
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Abstract
The present invention relates to technical field of ceramic material more particularly to a kind of preparation methods of silicon nitride composite powder.The preparation method of the silicon nitride composite powder includes the following steps: that S1,5:2.5-3 is added to the water in molar ratio by aluminum nitrate and yttrium nitrate, forms material solution；S2, urea is added in material solution, forms mixed solution；S3, beta-silicon nitride powder is added in mixed solution, forms mixture；S4: being heat-treated mixture, and heat treatment temperature is 25-99 DEG C, is separated by solid-liquid separation after heat treatment, and obtained solid dried object is silicon nitride composite powder.The preparation method of silicon nitride composite powder of the invention, not only simple process but also pH value is easy to control, convenient for promoting, in addition, it is uniform to coat the nanoscale sintering aid to be formed in silicon nitride surface.
Description
Technical field
The present invention relates to technical field of ceramic material more particularly to a kind of preparation methods of silicon nitride composite powder.
Background technique
The microstructure of ceramics determines the performance of ceramic material, and microstructure is different, and material property also can be significantly different.
Wherein, microstructural factor includes crystallite dimension, grain size distribution, grain morphology, crystal boundary composition, Grain Boundary Character distribution
Deng.Restriction of the microstructure by material component and material preparation process, then its microstructure is no doubt different for material component difference,
Material component is identical but material preparation process is different, then microstructure also can be different.Therefore, to the preparation process of ceramic material into
Row optimization, can improve the performance of ceramic material.
Traditional ceramics material preparation process generally comprises: four powder preparation, material mixing, molding and sintering basic steps.Powder
Body preparation has a great impact to ceramic material uniform microstructure.Mixing will affect ceramic material densification and micro- knot
The uniformity of structure.
For ceramic composite, using the method coated, this method can control the group of powder for composite granule preparation
Poly- state improves the mixture homogeneity of disperse phase and sintering aid, promotes the sintering of composite granule, and improve different in composite ceramics
State is combined, surface residual stress is reduced.
Silicon nitride ceramics is a kind of important ceramics, and nitrogen can be effectively improved by adding nanoscale sintering aid in silicon nitride
The performance of SiClx ceramics.
Currently, in silicon nitride there are mainly three types of the methods of addition nanoscale sintering aid: 1, it is being nitrogenized using dispersing agent
Nanoscale sintering aid is added in silicon；2, nanoscale sintering aid is added using ammonia water titration method in silicon nitride；3, using carbon
Sour hydrogen ammonium titration adds nanoscale sintering aid in silicon nitride.
A kind of preparation method of silicon nitride composite material of the prior art is, what Zheng Guangming, Zhao Jun, Zhou Yonghui etc. delivered
Sialon-Si3N4It is the design and preparation (Zheng Guangming, Zhao Jun, Zhou Yonghui etc. of gradient nano composite ceramic tool material
.Sialon-Si3N4It is the design and preparation [J] silicate journal of gradient nano composite ceramic tool material, 2011,39 (5):
783-788.).This method is by nano Si3N4With nanometer Al2O3After powder incorporates liquid phase dispersion medium (dehydrated alcohol) respectively, receive
Rice Si3N4Opposite nano Si is added in solution3N4The polyethylene glycol that the molecular weight of quality 0.5% is 4000, in nanometer Al2O3Solution
It is middle that opposite nanometer Al is added2O3The polyethylene glycol that the relative molecular mass that quality is 1.5% is 4000 is each configured to a nanometer material
Material accounts for the suspension that total mass fraction is 0.2%, and the pH value of each suspension is adjusted to 9.5-10.One existing for this method
Deficiency is, it is necessary to using the peptizaiton of dispersing agent, just can achieve finely dispersed purpose, so that nano-scale particle be avoided to exist
Agglomeration occurs in solution.
A kind of preparation method of silicon nitride composite material of the prior art is that Li Guobin is sent out in 2012 in Institutes Of Technology Of Nanjing
The injection forming of table prepares the technical research of high-performance silicon nitride ceramics.This method is by Y (NO3)3·6H2O and AlCl36H2O adds
Enter deionized water mixing, add ammonium hydroxide and adjust solution pH value to 10, then stirring a period of time, 85 DEG C of baking oven drying are added,
600 DEG C of calcinings later, obtain Al2O3-Y2O3Nanoscale sintering aid.A deficiency existing for this method is 1, ammonia water titration
It is difficult to control the uniformity of titration speed；2, pH value is unstable；3, the cladding presoma that ammonia water titration obtains is that point covers formula cladding,
It is not uniform one layer on silicon nitride matrix surface.
Summary of the invention
(1) technical problems to be solved
The purpose of the present invention is to provide a kind of preparation method of silicon nitride composite powder, the systems of the silicon nitride composite powder
Preparation Method not only simple process but also pH value is easy to control, convenient for promoting, in addition, coating the nanoscale to be formed in silicon nitride surface
Sintering aid is uniform.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
The present invention provides a kind of preparation method of silicon nitride composite powder.Specifically, the preparation of the silicon nitride composite powder
Method includes the following steps:
S1, by aluminum nitrate and yttrium nitrate, 5:2.5-3 is added to the water in molar ratio, forms material solution；
S2, urea is added in material solution, forms mixed solution；
S3, beta-silicon nitride powder is added in mixed solution, forms mixture；
S4: being heat-treated mixture, and heat treatment temperature is 25-99 DEG C, is separated by solid-liquid separation, is obtained after heat treatment
Solid dried object is silicon nitride composite powder.
Further, in S3, when beta-silicon nitride powder is added in mixed solution, silicon nitride and aluminum nitrate, yttrium nitrate
The molar ratio of mixture is 28:5.55-17.7.
Further, it in S3, when beta-silicon nitride powder is added in mixed solution, carries out at ultrasonic treatment and stirring in water bath
Reason.
Further, S4 includes the following steps:
S41: being heat-treated mixture, and keeps the temperature；
S42: room temperature will be cooled to by the mixture of S41 processing；
S43: centrifugal treating will be carried out by the mixture of S42 processing, obtains solid sediment；
S44: being dried the solid sediment that S43 is obtained, and obtains solid dried object.
Further, in S2, when urea is added in material solution, the mixture of urea and aluminum nitrate, yttrium nitrate
The minimum 20:1 of molar ratio.
Further, in S41, the mode of heat treatment is water-bath heat treatment, and the temperature of heat treatment is 95 DEG C, soaking time
For 1-4h.
Further, in S43, the mode of centrifugal treating is that repeatedly washing carries out multiple alcohol centrifugation after being centrifuged again.
Further, in S44, the mode of drying process is drying, and drying temperature is 60-100 DEG C.
Further, in S1, when aluminum nitrate and yttrium nitrate are added to the water, stirring in water bath processing is carried out.
The present invention also provides a kind of silicon nitride composite powder, silicon nitride composite powder is by above-mentioned silicon nitride composite powder
Preparation method is prepared.
(3) beneficial effect
The beneficial effects of the present invention are:
The preparation method of silicon nitride composite powder of the invention, aluminum nitrate and yttrium nitrate are added 5:2.5-3 in molar ratio
In water, when so that being sintered using silicon nitride composite powder prepared by the preparation method of silicon nitride composite powder of the invention, generate
Y3Al5012, Y3Al5012Enable to the silicon nitride composite powder prepared using the preparation method of silicon nitride composite powder of the invention
The ceramics that body sintering generates have excellent performance；
In the preparation method of silicon nitride composite powder of the invention, urea is added what aluminum nitrate and yttrium nitrate were formed with water
In material solution, mixed solution is formed, silicon nitride is added in mixed solution, forms mixture, when to the hot place of mixture progress
When reason, heat treatment temperature is 25-99 DEG C, and the urea in mixture, which will absorb heat, occurs hydrolysis, generates hydroxide ion, makes
Mixture is obtained into alkalinity；
In the preparation method of silicon nitride composite powder of the invention, the hydrolysis of urea be uniformly be dissolved in urea it is mixed
After closing in solution, occur when mixture heating, so the hydroxide ion that urea is generated through hydrolysis uniformly disperses
In the mixture, compare titration, and hydroxide ion disperses more uniform, does not need the uniformity of control titration speed,
Not only simple process but also pH value is easy to control, convenient for promoting；
In the preparation method of silicon nitride composite powder of the invention, the content of urea and water is fixed, the temperature of hydrolysis of urea
As soon as the hydroxide ion that urea water solves is fixed with time timing, by the temperature and time for controlling hydrolysis of urea
PH value is controlled, compare titration, and without controlling the amount of titration, pH value is easy to control, convenient for promoting；
In the preparation method of silicon nitride composite powder of the invention, hydrolysis of urea generate hydroxide ion and carbonate from
Son is evenly dispersed in the mixture, when being separated by solid-liquid separation separation, aluminium hydroxide that hydroxide ion and aluminium ion, ruthenium ion generate and
Yttrium hydroxide is evenly dispersed in the mixture, and the yttrium carbonate that carbanion and ruthenium ion generate is evenly dispersed in the mixture,
After aluminium hydroxide, yttrium hydroxide and yttrium carbonate encounter silicon nitride, nitridation will be coated on by matrix of alpha-silicon nitride powders particle
The surface layer of silicon, the clad that aluminium hydroxide, yttrium hydroxide and yttrium carbonate are formed is more evenly；
In the preparation method of silicon nitride composite powder of the invention, beta-silicon nitride powder is added in mixed solution, silicon nitride powder
The irregular surface of each particle of body can come into full contact with the mixed solution of liquid phase, when being separated by solid-liquid separation separation, mixture
In hydroxide ion, aluminium ion, ruthenium ion and carbanion will using each silicon nitride particle as matrix be sucked out generate
Aluminium hydroxide, yttrium hydroxide and yttrium carbonate are simultaneously coated on the irregular surface of silicon nitride particle, so in silicon nitride surface packet
The nanoscale sintering aid covered is uniform one layer；
In the preparation method of silicon nitride composite powder of the invention, urea precipitation from homogeneous solution coats silicon nitride particle,
As aluminium hydroxide, yttrium hydroxide and yttrium carbonate are constantly sucked out by matrix of silicon nitride, aluminium hydroxide, yttrium hydroxide and carbonic acid
Yttrium will silicon nitride irregular surface layer in layer coat, realize silicon nitride irregular surface carry out layer
Formula cladding is covered, so the nanoscale sintering aid in silicon nitride surface cladding is uniform one layer.
To sum up, the preparation method of silicon nitride composite powder of the invention, not only simple process but also pH value is easy to control, just
In popularization, in addition, it is uniform to coat the nanoscale sintering aid to be formed in silicon nitride surface.
Detailed description of the invention
Fig. 1 is the silicon nitride sinter that silicon nitride composite powder made from the embodiment of the present invention one obtains after being pre-sintered
X ray diffracting spectrum (XRD diagram)；
Fig. 2 is the silicon nitride sinter that silicon nitride composite powder made from the embodiment of the present invention two obtains after being pre-sintered
X ray diffracting spectrum (XRD diagram)；
Fig. 3 is the silicon nitride sinter that silicon nitride composite powder made from the embodiment of the present invention three obtains after being pre-sintered
X ray diffracting spectrum (XRD diagram)；
Fig. 4 is the scanning electron microscopy of the beta-silicon nitride powder under the 200nm scale before the embodiment of the present invention three is uncoated
(SEM) photo；
Fig. 5 is the scanning electron microscopy of the beta-silicon nitride powder under the 100nm scale before the embodiment of the present invention three is uncoated
(SEM) photo；
Fig. 6 is the scanning electron microscopy of the silicon nitride composite powder under 200nm scale made from the embodiment of the present invention three
(SEM) photo；
Fig. 7 is the scanning electron microscopy of the silicon nitride composite powder under 100nm scale made from the embodiment of the present invention three
(SEM) photo；
Fig. 8 is the silicon nitride sinter that silicon nitride composite powder made from the embodiment of the present invention four obtains after being pre-sintered
X ray diffracting spectrum (XRD diagram)；
Fig. 9 is the silicon nitride sinter that silicon nitride composite powder made from the embodiment of the present invention five obtains after being pre-sintered
X ray diffracting spectrum (XRD diagram)；
Figure 10 is the transmission electron microscopy of the beta-silicon nitride powder under the 500nm scale before the embodiment of the present invention five is uncoated
(TEM) photo；
Figure 11 is the transmission electron microscopy of the silicon nitride composite powder under 500nm scale made from the embodiment of the present invention five
(TEM) photo；
Figure 12 is the transmission electron microscopy of the silicon nitride composite powder under 50nm scale made from the embodiment of the present invention five
(TEM) photo；
Figure 13 is that the EDS carried out to silicon nitride composite powder made from the embodiment of the present invention five is detected；
Figure 14 is the transmission electron microscopy of the silicon nitride composite powder under 100nm scale made from the embodiment of the present invention five
(TEM) photo；
Figure 15 is electric for the transmission of element silicon in the silicon nitride composite powder under 200nm scale made from the embodiment of the present invention five
Micro- (TEM) photo of son；
Figure 16 is electric for the transmission of aluminium element in the silicon nitride composite powder under 200nm scale made from the embodiment of the present invention five
Micro- (TEM) photo of son；
Figure 17 is electric for the transmission of yttrium in the silicon nitride composite powder under 200nm scale made from the embodiment of the present invention five
Micro- (TEM) photo of son.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
The preparation method of silicon nitride composite powder of the invention includes the following steps:
S1, by aluminum nitrate and yttrium nitrate, 5:2.5-3 is added to the water in molar ratio, forms material solution；
S2, urea is added in material solution, forms mixed solution；
S3, beta-silicon nitride powder is added in mixed solution, forms mixture；
S4: being heat-treated mixture, and heat treatment temperature is 25-99 DEG C, is separated by solid-liquid separation, is obtained after heat treatment
Solid dried object is silicon nitride composite powder.
The preparation method of silicon nitride composite powder of the invention, the silicon nitride composite powder of preparation are silicon nitride and its surface layer
The sintering aid of cladding, sintering aid are aluminium hydroxide, yttrium hydroxide and yttrium carbonate.
The molar ratio of aluminum nitrate and yttrium nitrate is 5:2.5-3, when the molar ratio of aluminum nitrate and yttrium nitrate is less than 5:2.5,
When so that being sintered using silicon nitride composite powder prepared by the preparation method of silicon nitride composite powder of the invention, miscellaneous phase is generated
Y203And Y4Al209, Y203And Y4Al209Meeting is so that the ceramic degradation that silicon nitride composite powder produced by the present invention is sintered.
When the molar ratio of aluminum nitrate and yttrium nitrate is greater than 5:3, so that using the preparation method system of silicon nitride composite powder of the invention
When standby silicon nitride composite powder is sintered, miscellaneous phase Al is generated203, Al203Meeting is so that silicon nitride composite powder produced by the present invention is burnt
The degradation of the ceramics of knot.
Mixture is heat-treated, heat treatment temperature is 25-99 DEG C, when being heat-treated to mixture, urine
Element can absorb heat hydrolysis, and when the temperature of mixture is lower than 25 DEG C, the hydrolysis of urea is hardly happened, will not be to the pH value of mixture
It works, the purpose for adjusting mixture pH value is not achieved, when temperature is greater than 99 DEG C, since water can distil in mixture, destroy mixed
The liquid phase environment of object is closed, technique can not continue.
The preparation method of silicon nitride composite powder of the invention, aluminum nitrate and yttrium nitrate are added to the water, and it is molten to form raw material
Liquid, material solution provide aluminium ion and ruthenium ion for subsequent reactions.Urea is added in material solution, mixed solution is formed, is mixed
Conjunction solution provides hydroxide ion for subsequent reactions and prepares.Beta-silicon nitride powder is added in mixed solution, forms mixture, mixing
Object provides the matrix of cladding for post precipitation object.Mixture is heat-treated, so that hydrolysis of urea, is realized uniformly to mixing
Hydroxide ion needed for addition reaction in object.Mixture after Overheating Treatment is separated by solid-liquid separation, it is dry to extract solid
Object, solid dried object are the silicon nitride composite powder that preparation generates.
The preparation method of silicon nitride composite powder of the invention, aluminum nitrate and yttrium nitrate are added 5:2.5-3 in molar ratio
In water, when so that being sintered using silicon nitride composite powder prepared by the preparation method of silicon nitride composite powder of the invention, generate
Y3Al5012, Y3Al5012Enable to the silicon nitride composite powder prepared using the preparation method of silicon nitride composite powder of the invention
The ceramics that body sintering generates have excellent performance.
In the preparation method of silicon nitride composite powder of the invention, urea is added what aluminum nitrate and yttrium nitrate were formed with water
In material solution, mixed solution is formed, silicon nitride is added in mixed solution, forms mixture, when to the hot place of mixture progress
When reason, heat treatment temperature is 25-99 DEG C, and the urea in mixture, which will absorb heat, occurs hydrolysis, generates hydroxide ion, makes
Mixture is obtained into alkalinity.
In the preparation method of silicon nitride composite powder of the invention, the hydrolysis of urea be uniformly be dissolved in urea it is mixed
After closing in solution, occur when mixture heating, so the hydroxide ion that urea is generated through hydrolysis uniformly disperses
In the mixture, compare titration, and hydroxide ion disperses more uniform, does not need the uniformity of control titration speed,
Not only simple process but also pH value is easy to control, convenient for promoting.
In the preparation method of silicon nitride composite powder of the invention, the content of urea and water is fixed, the temperature of hydrolysis of urea
As soon as the hydroxide ion that urea water solves is fixed with time timing, by the temperature and time for controlling hydrolysis of urea
PH value is controlled, compare titration, and without controlling the amount of titration, pH value is easy to control, convenient for promoting.
In the preparation method of silicon nitride composite powder of the invention, hydrolysis of urea generate hydroxide ion and carbonate from
Son is evenly dispersed in the mixture, when being separated by solid-liquid separation separation, aluminium hydroxide that hydroxide ion and aluminium ion, ruthenium ion generate and
Yttrium hydroxide is evenly dispersed in the mixture, and the yttrium carbonate that carbanion and ruthenium ion generate is evenly dispersed in the mixture,
After aluminium hydroxide, yttrium hydroxide and yttrium carbonate encounter silicon nitride, nitridation will be coated on by matrix of alpha-silicon nitride powders particle
The surface layer of silicon, the clad that aluminium hydroxide, yttrium hydroxide and yttrium carbonate are formed is more evenly.
In the preparation method of silicon nitride composite powder of the invention, beta-silicon nitride powder is added in mixed solution, silicon nitride powder
The irregular surface of each particle of body can come into full contact with the mixed solution of liquid phase, when being separated by solid-liquid separation separation, mixture
In hydroxide ion, aluminium ion, ruthenium ion and carbanion will using each silicon nitride particle as matrix be sucked out generate
Aluminium hydroxide, yttrium hydroxide and yttrium carbonate are simultaneously coated on the irregular surface of silicon nitride particle, so in silicon nitride surface packet
The nanoscale sintering aid covered is uniform one layer.
In the preparation method of silicon nitride composite powder of the invention, urea precipitation from homogeneous solution coats silicon nitride particle,
As aluminium hydroxide, yttrium hydroxide and yttrium carbonate are constantly sucked out by matrix of silicon nitride, aluminium hydroxide, yttrium hydroxide and carbonic acid
Yttrium will silicon nitride irregular surface layer in layer coat, realize silicon nitride irregular surface carry out layer
Formula cladding is covered, so the nanoscale sintering aid in silicon nitride surface cladding is uniform one layer.
In S3, when beta-silicon nitride powder is added in mixed solution, silicon nitride and aluminum nitrate, yttrium nitrate mixture rub
You are than being 28:5.55-17.7.
When the molar ratio of silicon nitride and aluminum nitrate, the mixture of yttrium nitrate is less than 28:5.55, then it can make hydroxide
Aluminium, yttrium hydroxide and yttrium carbonate are excessive, excessive glass phase occur, lead to the preparation using silicon nitride composite powder of the invention
The ceramic performance that the silicon nitride composite powder of method preparation is sintered weakens, and especially mechanical property weakens.When silicon nitride and
Aluminum nitrate, yttrium nitrate mixture molar ratio be greater than 28:17.7 when, then can make aluminium hydroxide, yttrium hydroxide and yttrium carbonate
It is very few, silicon nitride surface layer coat thickness will thinning and uniformity can also be deteriorated.
In S3, when beta-silicon nitride powder is added in mixed solution, ultrasonic treatment and stirring in water bath processing are carried out.
The second order effect of ultrasonic wave is such as mechanical in ultrasonic treatment shakes, emulsifies, spreading, smashing that be all conducive to silicon nitride complete
Orientation, which is sufficiently mixed, to be added in mixed solution.Stirring in water bath processing can promote silicon nitride to be rapidly and uniformly diffused in mixed solution
In.
Specifically, S4 includes the following steps:
S41: being heat-treated mixture, and keeps the temperature；
S42: room temperature will be cooled to by the mixture of S41 processing；
S43: centrifugal treating will be carried out by the mixture of S42 processing, obtains solid sediment；
S44: being dried the solid sediment that S43 is obtained, and obtains solid dried object.
Wherein, in S2, when urea is added in material solution, mole of urea and aluminum nitrate, the mixture of yttrium nitrate
Than minimum 20:1, in S41, the mode of heat treatment is water-bath heat treatment, and the temperature of heat treatment is 95 DEG C, soaking time 1-
4h。
Urea is added in material solution, forms mixed solution, and mixed solution is not heat-treated, and water does not occur substantially for urea
Solution reaction, when being heat-treated to mixture, urea starts to hydrolyze, urea and aluminum nitrate, yttrium nitrate mixture mole
Than being more than or equal to 20:1, when the temperature of heat treatment is 95 DEG C, when soaking time 1-4h, the amount of the urea hydrolyzed be addition
A part of urea amount, and be one quantitative, the pH value of mixture is 7.9 at this time.Due to the concentration of hydrolysis of urea and urea, water
There is relationship in the time of the temperature and hydrolysis that solve reaction, so when the content of urea is enough, as long as control mixture
Heat treatment temperature and soaking time, the amount of hydrolysis of urea is just fixed, and then the pH value of mixture is fixed, so, if control
Heat treatment temperature and soaking time can control the pH value of mixture, and compare the prior art, and PH control mode is easy to operate,
And the controlling value of pH value is more accurate.
In S43, the mode of centrifugal treating is that repeatedly washing carries out multiple alcohol centrifugation after being centrifuged again.
It, can be by silicon nitride and aluminium hydroxide, yttrium hydroxide, carbonic acid after washing centrifugation and three times alcohol centrifugation three times
Yttrium, which is separated from the mixture, to be come, and good separating effect.
In S44, the mode of drying process is drying, and drying temperature is 60-100 DEG C.Drying and processing can make through S43
Obtained silicon nitride and aluminium hydroxide, yttrium hydroxide, yttrium carbonate superficial drying, separating effect is more preferable.
In S1, when aluminum nitrate and yttrium nitrate are added to the water, stirring in water bath processing is carried out.Preferably, speed of agitator is
300r/min.Stirring in water bath enables to aluminum nitrate and yttrium nitrate quickly to dissolve.
The present invention also provides a kind of silicon nitride composite powder, silicon nitride composite powder is by above-mentioned silicon nitride composite powder
Preparation method is prepared.
To sum up, the preparation method of silicon nitride composite powder of the invention, not only simple process but also pH value is easy to control, this
Outside, to coat the nanoscale sintering aid to be formed in silicon nitride surface uniform.
Embodiment one
S1, by aluminum nitrate and yttrium nitrate, 5:2.5 is added in 500ml deionized water in molar ratio, forms material solution；
S2, after aluminum nitrate and yttrium nitrate are completely dissolved, urea is rubbed by the mixture of urea and aluminum nitrate, yttrium nitrate
You form mixed solution than being that 20:1 is added in material solution；
S3, beta-silicon nitride powder is added in mixed solution by the molar ratio of silicon nitride and aluminum nitrate for 28:0.37, is carried out first
The ultrasonic treatment of 0.5h and the stirring in water bath of rear 0.5h are handled, and circulation three times, forms mixture；
S4: carrying out water-bath heat treatment to mixture, and keep the temperature, and the temperature of heat treatment is 95 DEG C, soaking time 4h；
S5: room temperature will be cooled to by the mixture of S4 processing；
S6: centrifugal treating will be carried out by the mixture of S5 processing, the mode of centrifugal treating is to wash after centrifugation again three times
It carries out alcohol three times to be centrifuged, obtains solid sediment；
S7: drying the solid sediment that S6 is obtained, and drying temperature is 80 DEG C, obtains solid dried object；
S8: in air atmosphere, being pre-sintered solid dried object, and the temperature of pre-sintering is 1150 DEG C, is nitrogenized
Silicon sintered body.
In the present embodiment, solid dried object made from S7 is after silicon nitride cladded aluminium hydroxide, yttrium hydroxide and yttrium carbonate
Obtained silicon nitride composite powder.Silicon nitride sinter made from S8 is the product after being sintered to silicon nitride composite powder.
Fig. 1 is that the X-ray for the silicon nitride sinter that the silicon nitride composite powder of the present embodiment S7 preparation obtains after S8 is pre-sintered is spread out
Penetrate map (XRD diagram), Fig. 1 show S8 preparation silicon nitride sinter in contain Y4Al2O9, silica and silicon nitride.Wherein,
Y4Al2O9It is impurity phase with silica.
Embodiment two
S1, by aluminum nitrate and yttrium nitrate, 5:2.7 is added in 500ml deionized water in molar ratio, forms material solution；
S2, after aluminum nitrate and yttrium nitrate are completely dissolved, urea is rubbed by the mixture of urea and aluminum nitrate, yttrium nitrate
You form mixed solution than being that 20:1 is added in material solution；
S3, beta-silicon nitride powder is added in mixed solution by the molar ratio of silicon nitride and aluminum nitrate for 28:0.37, is carried out first
The ultrasonic treatment of 0.5h and the stirring in water bath of rear 0.5h are handled, and circulation three times, forms mixture；
S4: carrying out water-bath heat treatment to mixture, and keep the temperature, and the temperature of heat treatment is 95 DEG C, soaking time 4h；
S5: room temperature will be cooled to by the mixture of S4 processing；
S6: centrifugal treating will be carried out by the mixture of S5 processing, the mode of centrifugal treating is to wash after centrifugation again three times
It carries out alcohol three times to be centrifuged, obtains solid sediment；
S7: drying the solid sediment that S6 is obtained, and drying temperature is 80 DEG C, obtains solid dried object；
S8: in air atmosphere, being pre-sintered solid dried object, and the temperature of pre-sintering is 1150 DEG C, is nitrogenized
Silicon sintered body.
In the present embodiment, solid dried object made from S7 is after silicon nitride cladded aluminium hydroxide, yttrium hydroxide and yttrium carbonate
Obtained silicon nitride composite powder, wherein aluminium hydroxide, yttrium hydroxide and yttrium carbonate cladding on silicon nitride with a thickness of 37-
66nm.Silicon nitride sinter made from S8 is the product after being sintered to silicon nitride composite powder.Fig. 2 is the present embodiment S7 system
The X ray diffracting spectrum (XRD diagram) for the silicon nitride sinter that standby silicon nitride composite powder obtains after S8 is pre-sintered, Fig. 2
Show to contain Y in the silicon nitride sinter of S8 preparation4Al2O9, silica and silicon nitride.Wherein, Y4Al2O9And silica
For impurity phase.
Embodiment three
S1, by aluminum nitrate and yttrium nitrate, 5:3 is added in 500ml deionized water in molar ratio, forms material solution；
S2, after aluminum nitrate and yttrium nitrate are completely dissolved, urea is rubbed by the mixture of urea and aluminum nitrate, yttrium nitrate
You form mixed solution than being that 20:1 is added in material solution；
S3, beta-silicon nitride powder is added in mixed solution by the molar ratio of silicon nitride and aluminum nitrate for 28:0.37, is carried out first
The ultrasonic treatment of 0.5h and the stirring in water bath of rear 0.5h are handled, and circulation three times, forms mixture；
S4: carrying out water-bath heat treatment to mixture, and keep the temperature, and the temperature of heat treatment is 95 DEG C, soaking time 3h；
S5: room temperature will be cooled to by the mixture of S4 processing；
S6: centrifugal treating will be carried out by the mixture of S5 processing, the mode of centrifugal treating is to wash after centrifugation again three times
It carries out alcohol three times to be centrifuged, obtains solid sediment；
S7: drying the solid sediment that S6 is obtained, and drying temperature is 80 DEG C, obtains solid dried object；
S8: under vacuum or inert gas, being pre-sintered solid dried object, and the temperature of pre-sintering is 650 DEG C, obtains
To silicon nitride sinter.
In the present embodiment, solid dried object made from S7 is after silicon nitride cladded aluminium hydroxide, yttrium hydroxide and yttrium carbonate
Obtained silicon nitride composite powder, wherein aluminium hydroxide, yttrium hydroxide and yttrium carbonate cladding on silicon nitride with a thickness of 37-
66nm.Silicon nitride sinter made from S8 is the product after being sintered to silicon nitride composite powder.Fig. 3 is the present embodiment S7 system
The X ray diffracting spectrum (XRD diagram) for the silicon nitride sinter that standby silicon nitride composite powder obtains after S8 is pre-sintered, the figure
Spectrum shows there was only silicon nitride in the silicon nitride sinter of S8 preparation, does not contain impurity phase.Fig. 4 (scale 200nm) and Fig. 5 (mark
Ruler is 100nm) be it is uncoated before beta-silicon nitride powder scanning electron microscopy (SEM) photo, Fig. 4 and Fig. 5 show silicon nitride powder
Body surface face is smooth, and Fig. 6 (scale 200nm) and Fig. 7 (scale 100nm) are electric for the scanning of silicon nitride composite powder made from S7
Micro- (SEM) photo of son, Fig. 6 and Fig. 7 show silicon nitride surface to generate the sintering aid of lint shape that (sintering aid is hydroxide
Aluminium, yttrium hydroxide and yttrium carbonate).
Example IV
S1, by aluminum nitrate and yttrium nitrate, 5:3 is added in 500ml deionized water in molar ratio, forms material solution；
S2, after aluminum nitrate and yttrium nitrate are completely dissolved, urea is rubbed by the mixture of urea and aluminum nitrate, yttrium nitrate
You form mixed solution than being that 20:1 is added in material solution；
S3, beta-silicon nitride powder is added in mixed solution by the molar ratio of silicon nitride and aluminum nitrate for 28:0.37, is carried out first
The ultrasonic treatment of 0.5h and the stirring in water bath of rear 0.5h are handled, and circulation three times, forms mixture；
S4: carrying out water-bath heat treatment to mixture, and keep the temperature, and the temperature of heat treatment is 95 DEG C, soaking time 3h；
S5: room temperature will be cooled to by the mixture of S4 processing；
S6: centrifugal treating will be carried out by the mixture of S5 processing, the mode of centrifugal treating is to wash after centrifugation again three times
It carries out alcohol three times to be centrifuged, obtains solid sediment；
S7: drying the solid sediment that S6 is obtained, and drying temperature is 80 DEG C, obtains solid dried object；
S8: under vacuum or inert gas, being pre-sintered solid dried object, and the temperature of pre-sintering is 850 DEG C, obtains
To silicon nitride sinter.
In the present embodiment, solid dried object made from S7 is after silicon nitride cladded aluminium hydroxide, yttrium hydroxide and yttrium carbonate
Obtained silicon nitride composite powder, wherein aluminium hydroxide, yttrium hydroxide and yttrium carbonate cladding on silicon nitride with a thickness of 37-
66nm.Silicon nitride sinter made from S8 is the product after being sintered to silicon nitride composite powder.Fig. 8 is the present embodiment S7 system
The X ray diffracting spectrum (XRD diagram) for the silicon nitride sinter that standby silicon nitride composite powder obtains after S8 is pre-sintered, the figure
Spectrum shows there was only silicon nitride in the silicon nitride sinter of S8 preparation, does not contain impurity phase.
Embodiment five
S1, by aluminum nitrate and yttrium nitrate, 5:3 is added in 500ml deionized water in molar ratio, forms material solution；
S2, after aluminum nitrate and yttrium nitrate are completely dissolved, urea is rubbed by the mixture of urea and aluminum nitrate, yttrium nitrate
You form mixed solution than being that 20:1 is added in material solution；
S3, beta-silicon nitride powder is added in mixed solution by the molar ratio of silicon nitride and aluminum nitrate for 28:0.37, is carried out first
The ultrasonic treatment of 0.5h and the stirring in water bath of rear 0.5h are handled, and circulation three times, forms mixture；
S4: carrying out water-bath heat treatment to mixture, and keep the temperature, and the temperature of heat treatment is 95 DEG C, soaking time 4h；
S5: room temperature will be cooled to by the mixture of S4 processing；
S6: centrifugal treating will be carried out by the mixture of S5 processing, the mode of centrifugal treating is to wash after centrifugation again three times
It carries out alcohol three times to be centrifuged, obtains solid sediment；
S7: drying the solid sediment that S6 is obtained, and drying temperature is 80 DEG C, obtains solid dried object；
S8: under vacuum or inert gas, being pre-sintered solid dried object, and the temperature of pre-sintering is 650 DEG C, obtains
To silicon nitride sinter.
In the present embodiment, solid dried object made from S7 is after silicon nitride cladded aluminium hydroxide, yttrium hydroxide and yttrium carbonate
Obtained silicon nitride composite powder, wherein aluminium hydroxide, yttrium hydroxide and yttrium carbonate cladding on silicon nitride with a thickness of 37-
66nm.Silicon nitride sinter made from S8 is the product after being sintered to silicon nitride composite powder.Fig. 9 is the present embodiment S7 system
The X ray diffracting spectrum (XRD diagram) for the silicon nitride sinter that standby silicon nitride composite powder obtains after S8 is pre-sintered, Fig. 9 table
It is bright, contain silicon nitride and Y in the silicon nitride sinter of S8 preparation3Al5O12, Y3Al5O12The property of silicon nitride sinter can be improved
Energy.Figure 10 (scale 500nm) is transmission electron microscopy (TEM) photo of uncoated preceding beta-silicon nitride powder, and Figure 10 shows nitrogen
SiClx powder surface is smooth.Figure 11 (scale 100nm) is the transmission electron microscopy (TEM) of silicon nitride composite powder made from S7
Photo, Figure 11 show silicon nitride surface generate lint shape sintering aid (sintering aid be aluminium hydroxide, yttrium hydroxide and carbon
Sour yttrium).Figure 12 (scale 50nm) is to shine the transmission electron microscopy (TEM) for carrying out obtaining after high power perspective at the midpoint Figure 11 1
Piece, it is the sintering aid of 37-66nm that Figure 12, which shows that there is a layer thickness on the surface of silicon nitride,.Figure 13 is to carry out to the point 1 in Figure 11
EDS testing result, Figure 13 illustrates ratio shared by each element.Figure 14 (scale 100nm) is to carry out at the midpoint Figure 11 1
Transmission electron microscopy (TEM) photo obtained after high power perspective, identifies dotted line position in Figure 14, obtains Figure 15, Figure 16
And Figure 17.Wherein, Figure 15 (scale 200nm) is the transmission electron microscopy to the silicon that dotted line indicating positions identifies in Figure 13
(TEM) photo, Figure 16 (scale 200nm) are the transmission electron microscopy to the aluminium that dotted line indicating positions identifies in Figure 13
(TEM) photo, Figure 17 (scale 200nm) are the transmission electron microscopy to the yttrium that dotted line indicating positions identifies in Figure 13
(TEM) photo, Figure 14, Figure 15, Figure 16 and Figure 17 show that solid dried object (silicon nitride composite powder) is by aluminium element made from S7
It is formed with yttrium, and element silicon is the matrix element of silicon nitride itself.
The SEM photograph of embodiment three and the TEM photo of embodiment five illustrate to have gone up one layer in the surface of silicon nitride cladding
Even sintering aid, the covered effect that sintering aid is coated on silicon nitride surface are fine.Embodiment one, embodiment two and embodiment
Three, five comparative illustration of example IV and embodiment, is pre-sintered does not obtain desired Y in air3Al5O12, only in vacuum
In and suitable sintering temperature under be sintered and can just access Y3Al5O12.Embodiment five illustrates the thickness of sintering aid in 37-66nm
In the range of, sintering aid thickness is suitable, and the covered effect that sintering aid is coated on silicon nitride surface is fine.
To sum up, the preparation method of silicon nitride composite powder of the invention, not only simple process but also pH value is easy to control, just
In popularization, in addition, it is uniform to coat the nanoscale sintering aid to be formed in silicon nitride surface.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (10)
1. a kind of preparation method of silicon nitride composite powder, which is characterized in that it includes the following steps:
S1, by aluminum nitrate and yttrium nitrate, 5:2.5-3 is added to the water in molar ratio, forms material solution；
S2, urea is added in the material solution, forms mixed solution；
S3, beta-silicon nitride powder is added in the mixed solution, forms mixture；
S4: being heat-treated mixture, and heat treatment temperature is 25-99 DEG C, is separated by solid-liquid separation after heat treatment, obtained solid
Dried object is silicon nitride composite powder.
2. the preparation method of silicon nitride composite powder according to claim 1, which is characterized in that
In S3, when beta-silicon nitride powder is added in mixed solution, the silicon nitride and the aluminum nitrate, the yttrium nitrate it is mixed
The molar ratio for closing object is 28:5.55-17.7.
3. the preparation method of silicon nitride composite powder according to claim 1, which is characterized in that
In S3, when beta-silicon nitride powder is added in mixed solution, ultrasonic treatment and stirring in water bath processing are carried out.
4. the preparation method of silicon nitride composite powder according to claim 1, which is characterized in that
S4 includes the following steps:
S41: being heat-treated mixture, and keeps the temperature；
S42: room temperature will be cooled to by the mixture of S41 processing；
S43: centrifugal treating will be carried out by the mixture of S42 processing, obtains solid sediment；
S44: being dried the solid sediment that S43 is obtained, and obtains solid dried object.
5. the preparation method of silicon nitride composite powder according to claim 4, which is characterized in that
In S2, when urea is added in the material solution, the urea and the aluminum nitrate, yttrium nitrate mixture rub
You are than minimum 20:1.
6. the preparation method of silicon nitride composite powder according to claim 5, which is characterized in that
In S41, the mode of heat treatment is water-bath heat treatment, and the temperature of heat treatment is 95 DEG C, soaking time 1-4h.
7. the preparation method of silicon nitride composite powder according to claim 4, which is characterized in that
In S43, the mode of centrifugal treating is that repeatedly washing carries out multiple alcohol centrifugation after being centrifuged again.
8. the preparation method of silicon nitride composite powder according to claim 1, which is characterized in that
In S44, the mode of drying process is drying, and drying temperature is 60-100 DEG C.
9. the preparation method of silicon nitride composite powder according to claim 1, which is characterized in that
In S1, when aluminum nitrate and yttrium nitrate are added to the water, stirring in water bath processing is carried out.
10. a kind of silicon nitride composite powder, which is characterized in that the silicon nitride composite powder is by any one of claim 1-9
The preparation method of the silicon nitride composite powder is prepared.
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| CN1827554A (en) * | 2006-02-09 | 2006-09-06 | 武汉理工大学 | Process for preparing coated ZrB2 composite powder |
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